Low calorie margarine substitute product



United States Patent 3,360,378 LOW CALORIE MARGARINE SUBSTITUTE PRODUCTJoseph George Spitzer, Mamaroneck, and Lloyd I. Osipow, New York, N.Y.

No Drawing. Continuation of application Ser. No. 515,253, Dec. 20, 1965.This application July 12, 1967, Ser. No. 652,666

20 Claims. (Cl. 99-123) ABSTRACT OF THE DISCLOSURE This inventionrelates to a low calorie margarine substitute product in the form of astable water-in oil emulsion. The margarine substitute product of theinvention has the flavor, body and functional characteristics ofconventional margarine, but is of a lower caloric content due to itshigher water and lower oil content than normal margarine.

The stable plastic edible margarine substitute composition of theinvention consists essentially of at least 45% by weight of water andfrom 20 to 55% oleaginous ingredients consisting essentially of anedible oil as the predominant oleaginous material and an emulsifyingsystern.

This application is a continuation application of copending applicationSer. No. 515,253 filed Dec. 20, 1965, now abandoned, which in turn, is acontinuation application of now abandoned Ser. No. 372,707 filed June 4,1964 which in turn is a continuation-in-part of now abandoned parentapplication Ser. No. 206,183 filed June 20, 1962.

This invention relates to a stable plastic edible lowcaloriemargarine-substitute product and method of producing same. A product ofthis type is intended to be eaten by people who wish to reduce theirintake of fat calories for reasons of health or appearance, withoutsacrificing their normal cooking and eating habits. A number ofdifiicult requirements must be met, if a low-caloriemargarine-substitute is to be acceptable to the general public.

A suitable low-calorie margarine-substitute must be manufactured fromnon-toxic ingredients. It should not only have the flavor of normalmargarine, but it also should have the body and functionalcharacteristics thereof. Accordingly, it should possess firmness in thecold to permit the manufacture of the margarine-substitute product inprint form and the slicing of patties. Then, too, it should be capableof retaining its solid characteristics at room temperature for anappreciable period of time, i.e. exhibit good stand-up qualities. Inaddition, it should melt rapidly at elevated temperatures, eg on hotfoods such as toast, vegetables, in a frying pan, such property beingcommonly referred to as the melting rate of the product. Moreover, suchproduct should be capable of melting in the mouth when themargarinesubstitute product is eaten as such or as a solid along withother food. Also, when used for shallow frying, a suitablemargarine-substitute product should act as a release agent.

The objects and advantages of the invention will be set forthhereinafter and in part will be obvious herefrom, or may be learned bypractice with the invention, the same being realized and attained bymeans of the compositions, steps and methods pointed out in the appendedclaims.

The invention consists of the novel compositions, steps and methodsherein described.

An object of this invention is to provide a margarine substitute productwhich has the flavor, body and functional characteristics of normalmargarine, but is of a lower caloric content. A further object of thisinvention is to provide a low-calorie margarine-substitute product whichhas the flavor, firmness, good stand-up qualities and quick-meltingproperties of normal margarine. Another object of this invention is toprovide a margarinesubstitute product, which when used for frying orbaking, acts as a releasing agent. A still further object of thisinvention is to provide a novel method for the manufacture of amargine-substitute product having the properties set forth in theforegoing objects.

It has been found that the objects of this invention may be realized byproducing a stable plastic edible margarine-substitute compositionhaving a flow point in the 1 range of 65 to 105 F., preferably to F.,and a penetrometer reading at 40 F. of 20 to 250, preferably 35 to 150,using a standard grease cone (3.2 cm. diameter, 45 angle, grams addedweight, 5 second interval), and being in the form of a water-in-oilemulsion.

, More particularly, the compositions of this invention contain anappropriate amount of water and from 20 to 55 percent by weight ofoleaginous ingredients consisting essentially of an edible oleaginousmaterial including 0.1 to 13% by weight of an oleaginous emulsifyingsystem selected from the group consisting of (a) emulsifying agentscontaining a component insoluble in both water and oil phases andpreferentially but incompletely wet by the oil ph-ase so as to give acontact angle greater than 90 but less than measured in the water phaseat the oil-water emulsifier film interface; and ('b) oil-solubleemulsifying agents that form a condensed film at the oil-waterinterface. The objectives of the invention are best obtained when wateris in an amount of at least equal to the weight of the oleaginouscomponents.

The term low-calorie as applied to the margarinesubstitute product ofour invention means that the caloric content of such product, comparedto conventional margarine, has been reduced in an amount at least 25%and, preferably, at least 40%. By the term conventional margarine asused herein, we mean a margarine having at least 80% by weight ofoleaginous components.

Products having the best mouth feel are those which have a melting orflow point at or below body temperature. In determining the flow pointof the low-calorie margarine-substitute products of this invention, thefollowing procedure was employed:

A 5 to 10 mg. sample previously conditioned to 65 F. is pressed lightlybetween two microscope cover glasses. The sample is placed on the hotplate of a Fisher-Johns melting point apparatus and the temperatureincreased to obtain approximate flow point range. When this range hasbeen determined, the heating element is turned off, and as thetemperature slowly drops, a fresh sample is placed in position and 30seconds allowed to observe product flow. This procedure is continuedusing fresh samples until the appropriate flow point (i.e. the samplejust barely flows in 30 seconds) is obtained.

As indicated hereinbefore, it is desirable that the lowcalorie margarineproducts of this invention have a suitable melting rate at elevatedtemperature. A procedure that may be used for determining melting rateis as follows:

(1) Place a 1" x 1%" x 1%" sample at 40 F. in a small frying pan. Thesample is placed on the square face. The frying pan is at 6575 F.

(2) Invert a small watch glass (approximately 2 inches in diameter,weight-62 gms.) and place it firmly on the sample.

(3) Place the frying pan containing the sample and watch glass on apreviously-heated hot plate set at low heat (Fisher, Heavy Duty HotPlate 660 watts).

(4) The height of the sample is measured when the frying pan contactsthe hot plate and the rate of slump is measured. A convenient Way to dothis is by placing a Koehler penetrometer with a dial calibrated inmillimeters (mm.), over the sample and bringing the needle stern incontact with the watch glass. The needle stem weighs 15.5 gms. Thereading of the penetrometer is recorded and measurements are made at15-second intervals.

(5) For convenience, the rate of melting is reported as the change inheight of the sample in mm. in a 60 second interval.

Low-calorie margarine-like products formed in accordance with thisinvention have a suitable melting rate, when tested by the aboveprocedure, when a sample of such product shows a reduction in height inthe range of 3 to 12 mm., and preferably 7 to 10 mm.

In the production of the margarine-like products of this inventioncontaining a lesser amount of oil than conventional margarine, onecannot merely use a lesser amount of oil but employ conventionaltechniques utilizing the components required by the standards ofidentity for margarine. To illustrate this point, in the United Statesthe inclusion of milk solids, equivalent milk derivatives or ground soybeans in conventional margarine is required by the standards of identityfor margarine. If this required concentration of milk solids is added tothe low-calorie products of our invention, the emulsion either becomesunstable or inverts to an oil-in-water emulsion. The same thing occursif other proteinaceous matter, e.g. soy proteinates, are substituted formilk solids. As will be described in detail hereinafter, this inventiondoes not preclude the utilization of special techniques whereby alow-calorie product may be obtained containing proteinaceous matter suchas milk solids.

Sulfoacetate derivatives of glyceryl esters of fatty acids are sometimesused as emulsifiers for conventional margarine. When employed in ourcompositions containing 55% or less fatty components, they have adeleterious effect even if milk solids are omitted.

Emulsifiers or combinations of emulsifiers allowable in conventionalmargarine that can be used in the practice of our invention are certaincombinations of lecithin with glyceryl esters of fatty acids. We havefound that these glyceryl esters may be monoor di-esters of 12 to 22carbon atom fatty acids or mixtures of these. However, they must besoluble in the margarine oil at the concentration used. Otherwise, theywill not form stable products. Glyceryl esters that have a high contentof glyceryl monostearate or glyceryl monopalmitate, e.g., more thanabout 50 percent, are insufficiently soluble in margarine oils and nonot form stable compositions in accordance with our invention, althoughthey are useful for preparing conventional margarines. Combinations ofthe preferred glyceryl esters and lecithin do not form stablewater-in-oil emulsions with less than 55 percent fatty material whenmilk solids are added.

Several possible reasons may be given why these emulsifier combinationsperform satisfactorily in conventional margarines containing about 15percent of water, but fail completely when the water content isincreased to about 45 percent or more. For one thing, the very highratio of oil to water in conventional margarines is overwhelminglyfavorable to the formation of water-in-oil emulsions. Reasonablysatisfactory emulsions can be prepared with this oil to water ratiowithout the addition of emulsifiers. Possibly free fatty acids andglyceryl diesters normally present in commercial margarine oils providesufficient emulsifying action.

Ionic emulsifiers, such as the sulfoacetate derivatives of glycerylesters and proteinates, including the caseinates found in milk, promotethe formation of oil-in-water emulsions. Consequently, the addition ofthese emulsifiers to water-in-oil emulsions containing a high amount ofwater, e.g., 50% water, causes the emulsions to break or invert.However, if only a small amount of water is present, these ionicemulsifiers are ionized to a lesser extent and do not fully exhibittheir tendency to promote the formation of oil-in-water emulsions. Also,as pointed out previously, the high oil to water ratio of conventionalmargarines is conducive to the formation of water-inoil emulsions. Wefind that the adverse effect of the addition of milk solids can bereduced by adding salts of multivalent cations, such as calciumchloride. This salt addition would have the effect of decreasing theionization of the proteinaceous material.

Lecithin and other phospholipids are amphoteric emulsifiers. At theirisoelectric point they provide an interfacial film that is electricallyneutral and should be conducive to the formation of water-in-oilemulsions. On either side of the isoelectric point, the interfacial filmwould be electrically charged and would promote the formation of thereverse type of emulsion. We find that while these phospholipids, oneither side of their isoelectric point, can be used as the soleemulsifier in the preparation of conventional margarines, they cannot beso employed in our compositions, which contain a high water content.Instead, we find that it is necessary to add an ancillary emulsifierthat is soluble in the margarine oil, is nonionizing, and is capable ofion-dipole interaction with the phospholipid. Examples of suchemulsifiers are stearic acid and glyceryl dioleate. We speculate thatthis ion-dipole interaction between the oil soluble, polar emulsifierand the phospholipid effectively screens the electrical charge of thephospholipid and thus favors the formation of a water-in-oil emulsion.

Glyceryl esters used in excess of their solubility in the margarine oilare useful emulsifiers for conventional margarines. However, they have adeleterious effect on our compositions. We have found that cast films ofthese glyceryl ester emulsifiers, instead of exhibiting a modestpreferential wetting by the oil phase, are practically completely wet bythe oil phase, displacing the water phase. Consequently, they do notfunction as effective emulsifiers.

Many oil soluble emulsifiers can be used alone in conventionalmargarines, but not in the compositions of our invention. Examples ofsuch emulsifiers are propylene glycol monostearate and glyceryldioleate. We have found that satisfactory compositions in accordancewith our invention can be prepared if we also add fatty acids, such asstearic or palmitic. The combination of these longchain fatty acids withhydroxy ester emulsifiers results in strong hydrogen bonds and theformation of condensed films at the water-oil interface.

The term condensed film refers to the physical state of thetwo-dimensional emulsifier phases at the oil-water interface.Two-dimensional phases are analogous to those in three dimensions, andmay be gaseous or condensed, i.e., liquid or solid. At the oil-waterinterphase, van der Waals interaction between the hydrocarbon chains ofthe emulsifier molecules is largely negated by the presence of the oilphase. Consequently, the interfacial film is generally gaseous. However,if there is strong interaction between the polar groups of theemulsifier molecules, the interfacial film is condensed. Surface phases,their characteristics, and methods for their determination are describedin a number of books dealing with surface chemistry, including: Harkins,W. D., The Physical Chemistry of Surface Films, New York, ReinholdPublishing Corp., 1952.

In the preferred embodiment of our invention we employ an emulsifyingagent that is insoluble in both the oil phase and the water phase and ispreferentially, but incompletely, wet by the oil phase. The terminsoluble is a relative one and refers to the condition of theemulsifier during the formation of the emulsion. If the concentration ofemulsifier and the temperature and other conditions of preparation ofthe emulsion are such that part of the emulsifier is not in solution,the emulisfier is characterized as an insoluble emulsifier. Lecithin issoluble in margarine oils. However, in the usual method of preparationof the compositions of our emulsion, the lecithin becomes hydrated andinsoluble in both phases.

We determine the wettability of an insoluble emulsifier by firstvspreading it on a glass microscope slide. We then immerse the slide inwater to allow the emulsifier film to become fully hydrate-d. The slidecoated with the hydrated emulsifier film is then transferred to a vesselpartially filled with the aqueous phase, previously warmed so that itstemperature is slightly above the melting point of the oil phase. Afterheating the oil phase to liquefy, it is poured gently over the waterphase. The contact angle formed by the two liquid phases and theemulsifier film is measured through the water phase. If the contactangle is greater than 90, the emulsifier film is preferentially wet bythe oil phase. If the contact angle is 180, the emulsifier film iscompletely wet by the oil phase.

In Table 1 we have listed examples of emulsifying agents that, whenhydrated, are insoluble in both oil and water phases, and can be used inthe practice of our invention. The examples in Table 1 includephospholipids and sorbitan monoesters of 12-22 carbon atom fatty acids.These insoluble emulsifiers are generally not preferentially wet by puremargarine oils. Consequently, they generally do not give stablewater-in-oil emulsions when the aqueous phase is about 45 percent ormore of the total composition. However, these insoluble emulsifier filmswill become preferentially, but incompletely, wet by the oil phase ifoil-soluble emulsifying agents are incorporated in the oil phase.

TABLE 1 Sorbitan monostearate Sorbitan monooleate Sorbitan monopalmitateSorbitan sesquioleate In Table 2 are examples of emulsifying agents thatare solublein margarine oils and can be used in combination with theinsoluble emulsifiers to obtain stable waterin-oil margarinesubstitutes. The examples of Table 2 are illustrative of 12-22 carbonatom fatty acids, their glyceryl esters and their sorbitan triesters.Commercial glyceryl monoesters and glyceryl diesters vary considerablyin composition. A commercial glyceryl diester may contain as muchmonoester as diester. Further, they are ordinarily esters of mixed fattyacids, with considerable variation in composition. One grade of glyceryldistearate may be soluble in a particular margarine oil, and othergrades may be insoluble. Both grades may be soluble in a differentmargarine oil. In selecting an emulsifier for use in combination with aninsoluble emulsifier from Table 1, the important criterion is that theemulsifier is soluble in the particular margarine oil selected.

TABLE 2 Oleic acid Palmitic acid Stearic acid Sorbitan trioleateSorbitan tripalmitate The insoluble and soluble emulsifiers are combinedin such proportions that when tested in a manner described hereinbefore,the insoluble emulsifier film is preferentially, but incompletely, wetby the oil phase. In the aforementioned insoluble and soluble emulsifiercombination, each component comprises at least percent by weight oftotal emulsifiers. With the more hydrophilic emulsifiers of Table 1,higher concentrations of oil-soluble emulsifiers (Table 2) are required.We may use as little as 0.1 percent or as much as 15 percent of theemulsifier combination. However, with the higher levels of emulsifierthe low-calorie. margarine substitute does not melt readily 6 in afrying pan, and the mouth feel is less satisfactory. Consequently, weprefer to use a minimum amount of the emulsifier combination, i.e., 0.1to 2 percent. At these low levels of emulsifier, more stable productsare obtained if more than half of the emulsifier is of the oil solubletype.

Also, as indicated hereinbefore, suitable emulsifier systems for thepractice of this invention are oil-soluble emulsifying agents, either asingle emulsifier or a combination of emulsifiers, that form a condensedfilm at the oil-water interface. We have discovered two general classesof oil-soluble emulsifier systems that can be used successfully in theabsence of insoluble emulsifiers as exemplified in Table 1. These are:(a) hydroxy esters of 12-22 carbon atom fatty acids containing at leasttwo hydroxyl groups that are not on adjacent carbon atoms. Thisrequirement avoids intramolecular hydrogen bonding. The sorbitantriesters of 12-22 carbon atom fatty acids are examples of emulsifiersmeeting these requirements. (b) Combinations of l222 carbon atom fattyacids and hydroxy esters of these fatty acids. Emulsifying systems ofthe aforedescribed type are generally used in an amount of 0.1 to 15% byweight, and preferably 0.3 to 10% by weight.

In Table 3 are examples of emulsifiers and emulsifier combinations thatare soluble in margarine oils and form a condensed film at the oil-waterinterface and produce stable water-in-oil emulsions. These are examplesof 1222 carbon atom fatty acids in combination with their glycerylmonoand di-esters, their propylene glycol monoesters and their sorbitantriesters, as well as the sorbitan triesters of these fatty acidswithout ancillary emulsifier. As noted hereinbefore, commercial hydroxyesters and margarine oils vary considerably in composition, and it isnecessary to select a grade of emulsifier that remains soluble in themargarine oil during the formation of the emulsion.

TABLE 3 Glyceryl monooleate. glycerlyl diollette. ropy eue g ycolmonostearate. ggfi'g igggf with Propylene glycol monopalmitste. OleicPronylene glycol monooleate.

Sorbitan triole-ite. Sorbitan tripalmitate. Sorbitan tristcarate.

At the same level of emulsifier, the systems containing an insolubleemulsifier produce more stable emulsions than those without a suitableinsoluble emulsifier. As indicated above, we may use from 0.1 to 15percent of the emulsifier combinations shown in Table 3. Preferably, weuse from 0.3 to 10 percent of emulsifier. In the case of combinations offatty acids with propylene glycol esters or glyceryl esters, theemulsions exhibit greater stability if the fatty acid componentconstitutes at least half of the emulsifier combination.

As stated hereinbefore, the physical state of the emulsifier systempreferably used in the practice of our invention consists of aninsoluble emulsifier component that is preferentially but incompletelywet by the oil phase. 'Where the insoluble emulsifier component is notpreferentially wet by the margarine oil, preferential wetting by the oilphase can be achieved by incorporating into the margarine oilemulsifiers that remain dissolved in the oil during the formation of theemulsion.

An alternative emulsifier system consists of emulsifying agents thatremain dissolved in the margarine oil during the formation of theemulsion, and which form a condensed interfacial film at the oil-waterinterface.

Emulsifier systems that may be used in the practice of this inventioninclude (a) a phospholipid insoluble in both Water and the oleaginousingredients in combination with a compound selected from the groupconsisting of 12-22 carbon atom fatty acids and hydroxy esters of apolyol with a 12-22 carbon atom fatty acid; (b) a 12-22 carbon atomfatty acid in combination with a hydroxyester of a polyol with a 12-22carbon atom fatty acid; (c) hydroxyesters of a polyol with a 12-22carbon atom fatty acid containing at least two hydroxy groups onnonadjacent carbon atoms; and (d) an hydroxy monoester of a polyol witha 12-22 carbon atom fatty acid that is insoluble in both the oil phaseand the water phase in combination with an oil soluble hydroxyester of apolyol with a 12-22 carbon fatty acid.

In the above-described systems (a), (b) and (d), the polyols arepreferably selected from the class consisting of propylene glycol,glycerol, sorbitan, monosaccharides and oligosaccharides. In all of thesystems mentioned above employing a combination of emulsifiers,preferably each component of the combination comprises at least percentof the total emulsifier content. In system (b) the fatty acid componentis preferably at least half of the emulsifier combination. In system (c)the oil-soluble component is preferably at least half of the emulsifiercombination.

In the compositions of this invention, conventional margarine additivesmay be added such as salt and other flavoring agent, coloring agents,preservatives, etc.

In the margarine-substitute products illustrated in the examples givenhereinafter, in addition to salt, the flavor employed may comprise anyof those that are accepted for use in edible products and frequentlycomprises diacetyl and other ketones, butyric acid and other acids,ethyl butyrate and other esters.

Examples of coloring agents useful in providing the desired color to themargarine-substitute product of this invention are carotene, annatto,etc.

Among the preservatives which may be incorporated in themargarine-substitute product of this invention are benzoic acid, sorbicacid and the appropriate salts of the foregoing acids.

Also, when desired, our products may include antioxidants that areacceptable for use in edible fats and oils. Among these are: normalpropyl gallate, the several tocopherols, butylated hydroxyanisole (BHA),butylated hydroxytoluene (BRT), nordihydroguaiaretic acid (NDGA).

As indicated hereinbefore, the oleaginous ingredients are in an amountfrom 20 to 55% :by weight and consist essentially of an oleaginousmaterial including 0.1 to 15% by weight of an emulsifying system. Theoleaginous material, exclusive of the emulsifying system, is generally aglyceride ester of a 12 to 22 carbon atom fatty acid, preferably atriglyceride ester of 16 to 18 carbon atom fatty acid; e.g. cottonseedoil. Of course, the oleaginous material may -be mixtures of esters ofthe aforedescribed type. Lower carbon atom fatty acid triglycerideesters such as cocoanut and palm kernal oil may also be judiciouslyemployed. Thes oils or fats may be i-somerized or modified and subjectedto selective or non-selective hydrogenation in varying degrees. The fator mixture of fats are typical of those used in conventional margarinetechnology.

When the low level of emulsifier is used, a higher m lting point fatshould be selected. Also, for better stability with lower emulsifyinglevels, homogenization and rapid cooling techniques are employed.

The following Examples A to H illustrate a number of different materialswhich may be used as the oleaginous component in accordance with thisinvention.

Example A Pressed palm kernal oil:

8 Example B Partially hydrogenated corn oil:

Melting point, F 103 Solid content index:

50 -F. 46.6 70 F. 32.6 90 F. 7.5

Example C Cottonseed oil:

Iodine value (approx) 108 !Free fatty acid, percent (max) .05

Example D A cocoanut oil rearranged with domestic vegetable oil:

Melting point, F. 92 Iodine value -50 Example E A rearranged hardenedcocoanut oil containing /2% lecithin:

Melting point, F. 94-96 Iodine value 1-2 Solid content index:

F. 64 70 F. 80 F. 39 92 F. 9 104 F. 0

Example F Partially hydrogenated corn oi-lA margarine oil in which oneportion of the oil is selectively hydrogenated to a degree in excess ofthat characacteristic of whole margarine fats and the other portion to acompensating lesser degree:

Melting point, F 94 Solid content index:

50 F. 26.5 14.4 80 F. 8.9 92 F. 2.3

Example G Margarine oil made from cott-onseed oil:

Melting point, F. 97 Free fatty acid, percent (max) .05 Solid contentindex:

50 IF. 27 70 F. 17 92 F. 4

Example H Partially hydrogenated corn oil:

Melting point, F 97 Solid content index:

70 F 24.9 80 F. 17.3 92 F. 5.7

Example I Hydrogenated cottonseed and soy oil:

Melting point, F 99 Solid content index:

50 F. 70 F. 70 F. 6-1

Example J Liquid corn oil:

Iodine value (approx) 123 Free fatty acid, percent (max) 0,05

Additional examples of materials useful as the oleaginous component arethe Wecobee oils which are hard butters produced from coconut oil. Theseoils contain a small amount (0.25%) of lecithin.

Examples of such oils are Wecobee W which has a MJP. of 94-96 F. with aniodine value of 10 max., and Weco bee R which has a MI. of 10110*3iF.with an iodine value of 4 max.

In general, the pH of the water phase is adjusted to 4 to 7. Thepreservative and color are added to the phase in which it is mostsoluble. Flavoring ingredients are generally added at the lowestpractical temperature. After preparing the separate oil and waterphases, the water phase is added slowly to the oil phase, with slowspeed agitation. The resulting emulsion may be then cooled further,homogenized, chilled and packaged appropriately.

A number of typical formulations are now given of margarine-substituteproducts formed in accordance with the present invention. In preparingsuch formulations, the following general procedure may be employed.

The oil phase and water phase are heated separately to a high enoughtemperature to melt or dissolve the components present. The water phaseis added slowly to the -oil phase while stirring with a laboratorystirrer. After complete addition of the water phase, stirring iscontinued at the highest speed that would avoid splashing. The resultingbatch is then agitated sufficiently to disperse the aqueous phase in theoil phase. The resulting emulsion may then be homogenized, chilled andpackaged appropri- 'ately.

The following is a detailed description of a specific method that may beused for the preparation of the lowcalorie margarine-substitute productsof this invention, following the general procedure outlined above.

(1) Mix and heat water and water-soluble components to desiredtemperature, e.g. 95 F.

(2) Mix and heat fat components and emulsifiers to 140 F. to ensurecomplete melting and, then, cool to desired mixing temperature, e.g. 95F.

(3) Weigh out 160 gins. of fat phase into a 600 ml. beaker (for a 40%fat product).

(4) With constant agitation at about 400 r.p.m. add 240 gms. of aqueousphase. The addition time should be 1 minute.

(5) As the water is added, the agitation is increased. Final speed isabout 900-l,000 r.p.m.

(6) Mix at the high speed for 3 minutes.

(7) At the end of the mixing, the sample is hand homogenized twice.

(8) The'product is collected in an aluminum mold approximately 1% x 1%"x 5" in which pre-folded foil laminated paper has been placed.

(9) The molded sample is held at 20 F. for 20-30 minutes and, then, thetemperature is increased to 40 F.

In all of the examples which follow, the amounts given are by weight.Following each of the examples, the flow point (RR) and penetrometerreading (P.R.) at 40 F. are given. In the examples wherever used,Centrophil IP is an example of a phospholipid material and has thefollowing composition:

Percent Chemical lecithin 2.5 Chemical cephalin 2O Inositol phosphatides38.5

Moisture and sugar 6 10 Preservative, color, flavor Sufficient F.P. F91-92 P.R. do 86 Example 2 Margarine oil of Example H percent 40Centrophil IP do 5 Palmitic acid do 5 Salt do 2.5 Water d0 47.5Preservative, color, flavor Sufficient F.P. F -92 P.R. do 87 Example 3Margarine oil of Example H percent 40 Sorbitan trioleate do.. 10 Salt do2.5 Water do 47.5 Preservative, color, flavor Sufiicient F.P. F 82-83P.R. do 87 Example 4 Margarine oil of Example H percent 40 Sorbitantrioleate do 8 Sorbitan monooleate do 2 Salt do 2.5 Water do 47.5Preservative, color, flavor Suflicient F.P. F 86-87 P.R. do 87 Example 5Margarine oil of Example H percent 40 Sorbitan trioleate do 5 Palmiticacid do 5 Salt do 2.5 Water do 47.5 Preservative, color, flavorSuflicient RP. F 88-90 P.R. do 65 Example 6 Margarine oil of Example Hpercent 15.0 Mixed fatty acids of corn oil (Emery 630) percent 4.0Centrophil IP do 1.0 Water do- 80.0 Preservative, color, flavorSutficient F.P. F 103.0 P.R. do 124 Example 7 Margarine oil of Example Hpercent 40 Sorbitan monopalmitate do 2 Palrnitic acid do 8 Salt do 2.5Water do 47.5 Preservative, color, flavor Suflicient RP. F 83-94 P.R. do37 Example 8 Margarine oil of Example A percent 7.5 Margarine oil ofExample C do 12.35 Margarine oil of Example H do 19.5 Centrophil IP do0.15 Stearic acid do 0.25 Palmitic acid do 0.25 Salt o 3.0 Water do 57.0Preservative, color, flavor Sufiicient F.P. F 89.6 P.R. do 83 1 1Example 9 Margarine oil of Example A percent 10.0 Margarine oil ofExample H do 29.1 Centrophil IP do .12 Stearic Aicd do .75 Salt do 2.5Water do 57.53 Preservative, color, flavor Sufficient RP. F 93.2 P.R do45 Example 10 Margarine oil of Example A percent 15.6 Margarine oil ofExample C do 24.0 Centrophil 1P do .15 Stearic Acid do 1.0 Salt do 2.5Water do 56.75 Preservative, color, flavor Sufiicient RP. F 96.8 P.R do83 Example 11 Margarine oil of Example A percent 15.0 Margarine oil ofExample C do 24.0 Centrophil IP do .14 Stearic Acid do .7 Salt do 2.5Water do 57.66 Preservative, color, flavor Suflicient F.P. F 83.0 P.R do75 Example 12 Margarine oil of Example A percent 10.0 Margarine oil ofExample C do 29.2 Centrophil IP do .35 Stearic Acid do .4 Salt do. 2.5Water do 57.55 Preservative, color, flavor Suificient F.P. F 65 P.R. do101 Example 13 Margarine oil of Example A percent 15.8 Margarine oil ofExample C do 23.7 Centrophil IP do .25 Stearic Acid do .25 Salt do 2.5Water do 57.5 Preservative, color, flavor Sufficient F.P F 72.5 P.R do86 Example 14 Margarine oil of Example A percent 7.5 Margarine oil ofExample C do 11.85 Margarine oil of Example H do 19.5 Centrophil IP do.15 Stearic Acid do .5 Palmitic Acid do .5 Salt do 3.0 Water d 57.0Preservative, color, flavor Sufficient F.P. F 95.0 P.R do 63 Example 15Margarine oil of Example A percent 7.5 Margarine oil of Example C do11.85 Margarine oil of Example H do 19.5 Centrophil IP do .15 StearicAcid do 1.0 Salt do 3.0

12 Water do 57.0 Preservative, color, flavor Sufficient F.P. F 93.2 P.Rdo 74 Example 16 Margarine oil of Example A percent 11.8 Margarine oilof Example C do 17.25 Margarine oil of Example H do 9.8 Centrophil IP do.15 Stearic Acid do 1.0 Salt do 3.0 Water do 57.0 Prcservative, color,flavor Suflicient F.P. F-.. 76 P.R do 98 Example 17 Margarine oil ofExample A percent 7.5 Margarine oil of Example H do 19.4 Margarine oilof Example C do 12.6 Centrophil IP do 0.1 Glyceryl Distearate (Kessler33D25) 1 do 0.3 Salt do 3.0 Lactose do 1.0 Water do 56.1 Preservative,color, flavor Suflicient F.P. F 80.6 P.R do 82 1 Kessler 33D25 is amixture of mono-, (li-, and trl-estcrs 0f stearlc acid pure) andglycerol.

Typical analysis:

Mono glyceride percent 14 Di glyceride do 66 Tri glyceride do 18.7Residual free fatty acid d0 0.7 Residual free glycerine do 0.6 Iodinevalue do 0.1 Melting point C 58.8

Example 18 Margarine oil of Example A "percent" 24 Margarine oil ofExample C do 11 Stearic acid do 4 Propylene glycol monostearate do 1Salt do 2.5 Water do 57.5 Prcservative, color, flavor Suflicient F.P. F93 P.R. do 64 Example 19 Margarine oil of Example H percent 24 Margarineoil of Example C do 11 Stearic acid d0 4 Glyceryl dioleostearate do 1Salt d0 2.5 Water do 57.5 Preservative, color, flavor Suflicient F.P. F93 P.R. do 68 Example 20 Margarine oil of Example H percent 26 Margarineoil of Example C do 11 Stearic acid do 2 Glyceryl monooleate (Myverol18-71E) do 1 Salt do 2.5 Water do 57.5

Example 21 Margarine oil of Example H percent 28.0 Margarine oil ofExample C do 11.5 Stearic acid do 0.34 Glyceryl Monooleate do 0.16

13 Salt percent 2.50 Water do 57.50 Preservative, color, flavorSufficient F F 82 4 P R do 91 Example 22 Margarine oil of Example Ape-rcent 15.8 Margarine oil of Example C do 23.7 Stearic acid do 0.4Centrophil LP. do 0.1 Salt do 3.2 Lactose do 3.0 Water do 53.8Preservative, color, flavor Suficient F P F 75 P R do 85 As indicatedheretofore, among the emulsifying systems useful in producing thelow-calorie margarine-substitute products of this invent-ion is thecombination of a 12-22 carbon atom fatty acid and/ or a phospholipid orand/or an hydroxyester of a polyol. With emulsifying systems of theaforementioned type, the level of emulsifying components may be quitelow, e.g. 0.1 to 0.5%, preferably 0.15 to 0.25%, by weight of the totallow calorie composition. When a fatty acid component is employed, it isgenerally in the range of 0.005 to 0.25% by weight, preferably .07 to.15%. Among the more preferred emulsifying systems employing a low levelof emulsifiers is the combination of a fatty acid, a phospholipid, andat least one hydroxyester of a 12-22 carbon atom fatty acid and a polyolselected from the group consisting of propylene glycol, glycerol,sorbitol, monosaccharides and oligosaccharides.

The following Examples 23 to 27 illustrate the use of emulsifyingsystems of the types mentioned above employing a low level ofemulsifying components.

Example 23 Margarine oil of Example I percent 19.00 Margarine oil ofExample B do 11.85 Margarine oil of Example I do 6.65 Butter fat do 0.50Stearic acid do 0.15 Centrophil LP. do 0.02 Propylene glycolmonostearate do 0.05 Color-concentrate do 0.004 Flavor (oil soluble) do0.04 Water do 56.146 Salt do 3.00 Lactose do 2.50 Flavor (water soluble)do 0.02 Preservative do 0.10 F.P. F 87 P.R. do 92 Example 24 Margarineoil of Example I percent 19.00 Margarine oil of Example B do 11.85Margarine oil of Example I do 6.65 Butter fat do 0.50 Stearic acid do0.15 Centrophil LP. -do 0.02 Monogylcerides of liquid cottonseed oil do0.07 Color-concentrate do 0.004 Flavor (oil soluble) do 0.04 Water do56.146 Salt do 3.00 Lactose do 2.50 Flavor (water soluble) do 0.02Preservative do 0.10 F.P. F 89 RR. do.. 7 95,

Example 25 Margarine oil of Example I percent 19.00 Margarine oil ofExample B do 11.85 Margarine oil of Example I do 6.65 Butter fat do 0.50Stearic acid do 0.15 Centrophil I.P. -do 0.02 Propylene glycolmonostearate do 0.05 Monogylcerides of liquid cottonseed oil do 0.07Color-concentrate do 0.004 Flavor (oil soluble) do 0.04 Water do 56.146Salt do- 3.00 Lactose do 2.50 Flavor (water soluble) do 0.02Preservative do 0.10 F.P. F 89 FR. do 98 Example 26 Margarine oil ofExample B percent 19.0 Margarine oil of Example I do 19.0 Propyleneglycol monostearate do 0.2 Decaglyceryl tristear-ate do 0.5Monoglycerides of liquid cottonseed oil d0 0.1 Color concentrate do0.004 Flavor (oil soluble) do 0.02 Water do 55.8 Salt do 2.8 Lactose doc 2.5 Preservative do 0.1 F P F 81 5 P R do 109 Example 27 Margarine oilof Example I percent 19.25 Margarine oil of Example B do 12.0 Margarineoil of Example I do 6.75 Centrophil LP. do 0.02 Propylene glycolmonostearate do 0.05 Monoglycerides of liquid cottonseed oil do .07Color concentrate do 0.004 Flavor (oil soluble) do 0.04 Water d-o 56.05Salt do 3.00 Lactose do 2.50 Flavor (water soluble) do .001 Preservativedo 0.10 F. P. F 89 RR. d0 95 In producing the low-caloriemargarine-substitute products of Examples 23-27, the same generalprocedure used in producing the products of Examples 1-22 is employed.More particularly, the water phase containing salt, lactose (sweetener),potassium sor-bate (preservative), water-soluble flavor and water isadded to the oil phase comprising the remaining components of each ofthe Examples 2327. The oil phase includes emulsifiers and the oil basestock. The resulting blend is mixed thoroughly to give a uniformemulsion after which the resulting emulsion is chilled and packaged.

The W/O emulsion products of Examples 23-27 contain low levels ofemulsifying components in order to obtain final products of optimummouth feel and melt down properties. Preferably, these compositions aremade in accordance with the method of copending application Ser. No.358,696 filed April 10, 1964 by Joseph George Spitzer, John I. Kearnsand Owen Cooper since it permits a wider latitude in the processingconditions that may be employed in obtaining a product of gooduniformity. The method of the aforementioned Spitzer et al. copendingapplication comprises the following steps: (1) forming a low-calorie,liquid, water-in-oil coarse emulsion comprismg a continuous oil phase ofan edible oil, and a dispersed water phase of water droplets consistingof at least 45 and not more than 80% by weight of the total composition;(2) subjecting said coarse emulsion to appropriate forces to produce afine emulsion which generally is of a higher viscosity than the coarseemulsion; and (3) converting the fine emulsion from a liquid to theplastic state by the quick-chilling thereof at a satisfactorycrystallization rate for the edible oil so that the resulting plasticemulsion is of a consistency where-by the plastic emulsion is capable ofbeing immediately packaged without causing emulsion breakdown.

A detailed description of the aforedescribed Spitzer et al. method forproducing the low-caloried products of Examples 23 to 27 is now given: Acoarse W/O emulsion is formed by intimately mixing, in suitable amountsand at appropriate temperatures, an oil phase containing an edible oilcomponent and a water phase. In order to ensure complete emulsificationit is desirable that when one phase is added to the other, e.g. addingthe water phase to the oil phase, there be employed adequate agitationas well as a controlled rate of mixing, e.g. adding 3% of the waterphase per minute. Also, both the water phase and oil phase when mixedshould be at an elevated temperature to ensure proper mixing. Forexample, the water phase may be at a temperature in the range of 50 to105 F., e.g. 86 F. and the oil phase at a temperature in the range of 80to 140 F., e.g. 95 F. After the initial formation of the W/O emulsion,the emulsion is held at an elevated temperature for a sufiicient periodof time with continuous mixing to ensure the production of a uniformblend in the form of a coarse W/O emulsion. The coarse emulsion ismaintained within a temperature of 73113 F., e.g. 8688 F., to ensureemulsion stability.

The coarse emulsion is then subjected to appropriate forces to produce afine emulsion, whose water droplets are of a reduced size, and which isof a higher viscosity than the coarse emulsion. More particularly, thecoarse emulsion is subjected to shearing forces by passing it to lacolloid mill, e.g. to a Manton-Gaulin colloid mill at 0.035 inchopening. The resulting fine emulsion is then quickchilled at a suitablerate, e.g. 0.1 to 3 F. per second, such as 1 F. per second, by feedingit through a scraped surface heat exchanger, e.g. a Votator, to convertit to a plastic product. Generally, the temperature at which the chilledemulsion assumes an appropriate consistency is 5072 F., e.g. 59 F. Theresulting plastic emulsion is then passed to conventional packagingequipment.

The low-calorie products of Examples 2327 containing a low level ofemulsifiers exhibit good stability, packing performance and usecharacteristics, including particularly good melt-down and mouth feelcharacteristics. In order to improve the margarine-like appearance ofsuch compositions upon melting in frying applications, a small amount(e.g. 0.01 to 0.2% of the final composition) of a water-dispersible gummay be incorporated in the composition to maintain the desired viscosityof the aqueous phase upon melting of the emulsion. The gum may be addedto the oil phase or the water phase prior to forming the emulsion.Examples of gums suitable for this purpose tare ribbon tragacanth, gumguar, agar-agar, etc.

The invention in its broader aspects is not limited to the specificcompositions described but departures may be made therefrom within thescope of the accompanying claims without departing from the principlesof the invention and without sacrificing its chief advantages.

What is claimed is:

1. A stable plastic edible low-calorie margarine-substitute compositionsubstantially free of non-modified proteinaceous matter and in the formof a water-in-oil emulsion having a flow temperature in the range of 65to 105 F. and a penetrometer reading at 40 F. of 20 to 250, saidcomposition consisting essentially of at least 45% by weight of waterand from 20 to 55% by weight of oleaginous ingredients consistingessentially of an edible oil as the predominant oleaginous material andan emulsifying system in an amount of 0.1 to 15% by weight of the totalcomposition selected from the group consisting of (a) a phospholipidinsoluble in both water and the oleaginous ingredients in combinationwith a compound selected from the group consisting of 12-22 carbon atomfatty acids and hydroxy esters of a polyol selected from the classconsisting of propylene glycol, glycerol, sorbitan, monosaccharides andoligosaccharides with a 12-22 carbon atom fatty acid; (b) a 12-22 carbonatom fatty acid in combination with a hydroxyester of a polyol selectedfrom the class consisting of propylene glycol, glycerol, sorbitol,monosaccharides and oligosaccharides with a 1222 carbon atom fatty acid;(c) hydroxyesters of sorbitan with a 12-22 carbon atom fatty acidcontaining at least two hydroxy groups on nonadjacent carbon atoms; and(d) an hydroxy monoester of a polyol selected from the class Consistingof propylene glycol, glycerol, sorbitan, monosaccharides andoligosaccharides with a 12-22 carbon atom fatty acid, said monoesterbeing insoluble in both the oil phase and the water phase, and being incombination with an oil soluble hydroxyester of a polyol selected fromthe class consisting of propylene glycol, glycerol, sorbitan,monosaccharides and oligosaccharides with a 1222 carbon fatty acid.

2. A stable plastic edible low-calorie margarine-substitute compositionaccording to claim 1, wherein the composition has a penetrometer readingat 40 F. in the range of 35 to 150.

3. A stable plastic edible low-calorie margarine-substitute compositionaccording to claim 1, wherein the composition has a flow temperature inthe range of to F. l

4. A stable plastic edible low-calorie margarine-su stitute compositionaccording to claim 1, where the edible oil is a glyceride ester of a 12to 22 carbon atom fatty acid. l -i 5. A stable plastic ediblelow-calorie margarine-substitute composition according to claim 1,wherein the emulsifying system is in an amount from 0.1 to 2% by weightof the total composition and is a combination of a phospholipid and a1222 carbon atom fatty acid and wherein at least half of the emulsifiercombination by weight is the fatty acid.

6. A stable plastic edible low-calorie margarine-substitute compositionaccording to claim 1, wherein the emulsifying system is in an amountfrom 0.1 to 2% by weight of the total composition and is a combinationof a phospholipid and an hydroxy ester of a polyol with a 12-22 carbonatom fatty acid selected from the group consisting of glycerylmonoesters, propylene glycol monoesters and glyceryl diesters andwherein at least half of the emulsifier combination by weight is thehydroxyester.

7. A stable plastic edible low-calorie margarine-substitute according toclaim 1, wherein the emulsifier system is in an amount from 0.3 to 10%by weight of the total composition and is a combination of a 12-22carbon fatty acid and a hydroxyester derived from a polyol with a 1222carbon atom fatty acid said polyol being selected from the groupconsisting of propylene glycol, glycerol, sorbitan, monosaccharides andoligosaccharides and wherein at least half of the emulsifier combinationby weight is the fatty acid.

8. A- stable plastic low-calorie margarine-substitute according toclaim1, wherein the emulsifying system is in an amount from 0.3 to 10% byweight of the total composition and is a sorbitan triester of a 12-22carbon atom fatty acid.

9. A stable plastic low-calorie margarine-substitute compositionaccording to claim 1, wherein the emulsifying system is in an amountfrom 0.3 to 10% by weight of the total composition and is a combinationof a sorbitan monoester of a 1222 carbon atom fatty acid and anotherhydroxyester of a polyol with a 12-22 carbon atom fatty acid selectedfrom the group consisting of glyceryl mono- BSteTS, P PY W g y olmonoesters and glyceryl diesters,

17 and wherein at least half of the emulsifier combination by weight isthe latter hydroxyester.

10. A stable plastic low-calorie margarine-substitute compositionaccording to claim 1, wherein the emulsifying system is the combinationof a 12-22 carbon atom fatty acid, a phospholipid and a hydroxyester ofa polyol with a 12-22 carbon atom fatty acid said polyol being selectedfrom the group consisting of propylene glycol, glycerol, sorbitan,monosaccharides and oligosaccharides.

11. A stable plastic low-calorie margarine-substitute compositionaccording to claim 1, wherein the emulsifying components are in anamount of 0.10 to 0.50% by weight of the total composition with thefatty acid component being in the range of 0.005 to 0.25% by weight.

12. A stable plastic low-calorie margarine-substitute composition havingthe following composition in parts by weight:

Margarine oil 39.5 Stearic acid .25 Palmitic acid .25 Salt 3.0 Water56.85 Phospholipid material .15

wherein the phospholipid material has the following analysis in percentby weight:

Chemical lecithin 2.5 Chemical cephalin 20 Inositol phosphatides 38.5Moisture and sugar 6 Cottonseed oil carrier 33 13. A stable plasticedible low-calorie margarine-substitute composition having the followingcomposition in parts by weight:

Margarine oil 38.00 Stearic acid 0.15 Propylene glycol mono stearate0.05 Water 56.1 Lactose 2.5 Salt 3.0 Phospholipid material .02

wherein the phospholipid material has the following analysis in percentby weight:

Chemical lecithin 2.5 Chemical cephalin 20 Inositol phosphatides 38.5Moisture and sugar 6 Cottonseed oil carrier 33 14. A stable plasticedible low-calorie margarine-substitute composition having the followingcomposition in parts by weight:

wherein the phospholipid material has the following analysis in percentby weight:

Chemical lecithin 2.5 Chemical cephalin 20 Inositol phosphatides 38.5Moisture and sugar 6 Cottonseed oil carrier 33 18 15. A stable plasticedible low-calorie margarine-substitute composition having the followingcomposition in parts by weight:

Margarine oil 38.00 Stearic acid 0.15 Propylene glycol mono stearate0.05 Monoglycerides of liquid cottonseed oil 0.07 Water 5 6.1 Lactose2.5 Salt 3.0 Phospholipid material .02

wherein the phospholipid material has the following analysis in percentby weight:

Chemical lecithin 2.5 Chemical cephalin 20 Inositol phosphatides 38.5Moisture and sugar 6 Cottonseed oil carrier 33 16. A stable plasticedible low-calorie margarine-substitute composition having the followingcomposition in parts by weight:

Margarine oil 38.00 Propylene glycol mono stearate 0.05 Monoglyceridesof liquid cottonseed oil 0.07 Water 56.05 Lactose 2.05 Salt 3.0Phospholipid material .02

wherein the phospholipid material has the following analysis in percentby weight:

Chemical lecithin 2.5 Chemical cephalin 20 Inositol phosphatides 38.5Moisture and sugar 6 Cottonseed oil carrier 33 17. A stable plasticedible low-calorie margarine substitute composition according to claim 6wherein the hydroxy ester is a glyceryl monoester.

18. A stable plastic edible low-calorie margarine substitute compositionaccording to claim 6 wherein the hydroxy ester is a glyceryl diester.

19. A stable plastic edible low-calorie margarine substitute compositionaccording to claim 18 wherein the glyceryl diester is glyceryldistearate.

20. A stable plastic edible low-calorie margarine substitute compositionhaving the following composition in parts by weight:

Margarine oil 39.5 Glyceryl distearate 0.3 Salt 3.0 Lactose 1.0 Water56.1 Phospholipid 0.1

wherein the phospholipid material has the following analysis in percentby weight:

(Other references on following page) 19 UNITED STATES PATENTS 3,096,2497/1963 Prigal 167-66 3,223,532 12/1965 Pinkalla et a1. 99-123 3,232,7652/1966 Rosenthal et a1. 99-118 X OTHER REFERENCES Gritfen, W. C.,Cosmetics: Science and Technology, Interscience Publ., N.Y. 1957, pp.998-1032, pp. 1012, 1029 relied on.

MAURICE W. GREENSTEIN, Primary Examiner.

1. A STABLE PLASTIC EDIBLE LOW-CALORIE MARGARINE-SUBSTITUTE COMPOSITIONSUBSTANTIALLY FREE OF NON-MODIFIED PROTEINACEOUS MATTER AND IN THE FORMOF A WATER-IN-OIL EMULSION HAVING A FLOW TEMPERATURE IN THE RANGE OF 65TO 105* F., AND A PENTROMETER READING AT 40*F. OF 20 TO 250, SAIDCOMPOSITION CONSISTING ESSENTIALLY OF AT LEAST 45% BY WEIGHT OF WATERAND FROM 20 TO 55% BY WEIGHT OF OLEAGINOUS INGREDIENTS CONSISTINGESSENTIALLY OF AN EDIBLE OIL AS THE PREDOMINANT OLEAGINOUS MATERIAL ANDAN EMULSIFYING SYSTEM IN AN AMOUNT OF 0.1 TO 15% BY WEIGHT OF THE TOTALCOMPOSITION SELECTED FROM THE GROUP CONSISTING OF (A) A PHOSPHOLIPIDINSOLUBLE IN BOTH WATER AND THE OLEAGINOUS INGREDIENTS IN COMBINATIONWITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF 12-22 CARBON ATOMFATTY ACIDS AND HYDROXY ESTERS OF A POLYOL SELECTED FROM THE CLASSCONSISTING OF PROPYLENE GLYCOL, GLYCEROL, SORBITAN, MONOSACCHARIDES ANDOLIGOSACCHARIDES WITH A 12-22 CARBON ATOM FATTY ACID; (B) A 12-22 CARBONATOMS FATTY ACID IN COMBINATION WITH A HYDROXYEYESTER OF A POLYOLSELECTED FROM THE CLASS CONSISTING OF PROPYLENE GLYCOL, GLYCEROL,SORBITOL, MONOSACCHARIDES AND OLIGSACCHARIDES WITH A 12-22 CARBON ATOMSFATTY ACID; (C) HYDROXYESTERS OF SORBITAN WITH A 12-22 CARBON ATOM FATTYACID CONTAINING AT LEAST TWO HYDROXY GROUPS ON NONADJACENT CARBON ATOMS;AND (D) AN HYDROXY MONOESTER OF A POLYOL SELECTED FROM THE CLASSCONSISTING OF PROPYLENE GLYCOL, GLYCEROL, SORBITAN, MONOSACCHARIDES ANDOLIGOSACCHARIDES ITH A 12-22 CARBON ATOM FATTY ACID, SAID MONOESTERBEING INSOLUBLE IN BOTH THE OIL PHASE AND THE WATER PHASE, AND BEING INCOMBINATION WITH AN OIL SOLUBLE HYDROXYESTER OF A POLYOL SELECTED FROMTHE CLASS CONSISTING OF PROPYLENE GLYCOL, GLYCEROL, SORBITAN,MONOSACCHARIDES AND OLIGOSACCHARIDES WITH A 12-22 CARBON FATTY ACID.